US4322558A - Oxidation process - Google Patents
Oxidation process Download PDFInfo
- Publication number
- US4322558A US4322558A US05/857,971 US85797177A US4322558A US 4322558 A US4322558 A US 4322558A US 85797177 A US85797177 A US 85797177A US 4322558 A US4322558 A US 4322558A
- Authority
- US
- United States
- Prior art keywords
- cyclohexane
- heavy metal
- metal compound
- cyclohexanol
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title claims description 18
- 238000007254 oxidation reaction Methods 0.000 title abstract description 12
- 230000003647 oxidation Effects 0.000 title abstract description 11
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 20
- 150000001639 boron compounds Chemical class 0.000 claims abstract description 8
- 239000007789 gas Substances 0.000 claims abstract description 7
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 32
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 22
- 150000002736 metal compounds Chemical class 0.000 claims description 19
- FGGJBCRKSVGDPO-UHFFFAOYSA-N hydroperoxycyclohexane Chemical compound OOC1CCCCC1 FGGJBCRKSVGDPO-UHFFFAOYSA-N 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 235000010338 boric acid Nutrition 0.000 claims description 12
- 238000004821 distillation Methods 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 7
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 229910001882 dioxygen Inorganic materials 0.000 claims description 5
- 239000007791 liquid phase Substances 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 125000005619 boric acid group Chemical class 0.000 claims description 4
- 150000001845 chromium compounds Chemical class 0.000 claims description 4
- 150000001869 cobalt compounds Chemical class 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 abstract description 9
- 239000004327 boric acid Substances 0.000 abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 5
- 230000007062 hydrolysis Effects 0.000 abstract description 5
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 5
- 239000001301 oxygen Substances 0.000 abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 abstract description 5
- 239000003054 catalyst Substances 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 150000001844 chromium Chemical class 0.000 abstract 1
- 229960002645 boric acid Drugs 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000000354 decomposition reaction Methods 0.000 description 6
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VGTPKLINSHNZRD-UHFFFAOYSA-N oxoborinic acid Chemical compound OB=O VGTPKLINSHNZRD-UHFFFAOYSA-N 0.000 description 4
- 150000002978 peroxides Chemical group 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- RPBPCPJJHKASGQ-UHFFFAOYSA-K chromium(3+);octanoate Chemical compound [Cr+3].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O.CCCCCCCC([O-])=O RPBPCPJJHKASGQ-UHFFFAOYSA-K 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- WZRXFPOWHQQSRJ-UHFFFAOYSA-N cyclohexyloxyboronic acid Chemical class OB(O)OC1CCCCC1 WZRXFPOWHQQSRJ-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-M hydroperoxide group Chemical group [O-]O MHAJPDPJQMAIIY-UHFFFAOYSA-M 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- XDVOLDOITVSJGL-UHFFFAOYSA-N 3,7-dihydroxy-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound O1B(O)OB2OB(O)OB1O2 XDVOLDOITVSJGL-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- KUGSJJNCCNSRMM-UHFFFAOYSA-N ethoxyboronic acid Chemical compound CCOB(O)O KUGSJJNCCNSRMM-UHFFFAOYSA-N 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000005474 octanoate group Chemical group 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
- C07C29/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups with molecular oxygen only
- C07C29/52—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups with molecular oxygen only in the presence of mineral boron compounds with, when necessary, hydrolysis of the intermediate formed
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/53—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition of hydroperoxides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Definitions
- This invention relates to the oxidation of cycloalkanes to cycloalkanols and cycloalkanones.
- a process for the manufacture of cyclohexanol and cyclohexanone comprises oxidising cyclohexane in the liquid phase with a molecular oxygen-containing gas in the presence of a boron compound with partial conversion of cyclohexane to give an oxidate comprising cyclohexane, boric esters of cyclohexanol and cyclohexylhydroperoxide, treating the said oxidate with water to hydrolyse the said boric esters to cyclohexanol and boric acids, separating the water and boric acids and treating the organic residue with a cyclohexane-soluble peroxide- decomposing heavy metal compound to decompose the cyclohexylhydroperoxide, and separating cyclohexane from the resulting cyclohexanol and cyclohexanone.
- the oxidation of cyclohexane in the liquid phase with a molecular oxygen-containing gas in the presence of a boron compound to give cyclohexanol and cyclohexanone is already known and is described, for example, in British Patent Specifications Nos. 996,791 and 996,792 and the oxidation stage of our process follows this prior art teaching.
- the molecular oxygen-containing gas may be oxygen itself but is preferably a mixture of oxygen with an inert gas, for example nitrogen.
- Air is a particularly convenient gas mixture to use, although mixtures of air with oxygen or nitrogen and therefore having a higher or lower oxygen content than air itself may also be used.
- the boron compound is preferably metaboric acid or dehydrated forms of orthoboric acid, but may be boron oxide, tetraboric acid or borate esters such as cyclohexyl metaborate, or methyl or ethyl borate.
- the boron compound is generally employed in amounts of at least 1 mole of boron compound (expressed as metaboric acid) per 6 moles of cyclohexane oxidised.
- the degree of conversion of the cyclohexane is generally from 4% to 25%.
- the oxidation temperature is generally from 140° to 180° C., preferably from 160° to 170° C., the pressure being at least sufficient to keep the cyclohexane substantially in the liquid phase, pressures up to about 50 bar being contemplated.
- Water is formed during the oxidation reaction, and it is desirable to remove water as it is formed to prevent the formation of higher hydrates of boric acid, by distilling off water, possibly together with some cyclohexane, as the oxidation proceeds.
- British Patent Specification No. 996,791 prescribes a maximum partial pressure of water over the reaction mixture for optimum results.
- the oxidate (other than unconverted cyclohexane) consists primarily of cyclohexyl borates. It also contains small amounts of cyclohexanone (up to about 10% of the cyclohexane converted) and of cyclohexyl hydroperoxide (up to 20% or more of the cyclohexane converted), and small amounts of by-products. It is then convenient to remove a part of the cyclohexane, conveniently in a flash column and at the same time reducing the pressure near to that of the atmosphere. The oxidate is then treated with water to hydrolyse the cyclohexyl borates to cyclohexanol and boric acid, again according to prior art teaching.
- Treatment takes place at temperatures above about 50° C., and results in an organic portion containing cyclohexane, cyclohexanol, cyclohexanone and cyclohexylhydroperoxide, and an aqueous portion consisting of a solution or suspension of boric acid, and also containing water-soluble by-products.
- the boric acid after suitable treatment may be recycled to the oxidation.
- Such treatment may include a purge to reduce the level of impurities, and dehydration to bring the boric acid to the level of hydration desired for the oxidation process.
- the organic residue is then treated with a cyclohexane-soluble peroxide-decomposing heavy metal compound to decompose the cyclohexyl-hydroperoxide.
- Preferred heavy metal compounds are cobalt compounds and more especially chromium compounds.
- the heavy metal compounds should be soluble in cyclohexane, and particularly preferred are salts of aliphatic or cycloaliphatic carboxylic acids, especially those having from 5 to 12 carbon atoms, or of mixtures thereof. Examples of particularly suitable salts of this kind are cobalt or chromium naphthenate or octoate.
- the heavy metal compound is preferably added to the organic residue as a solution in a hydrocarbon, for example in white spirit, but more especially in cyclohexane itself.
- the amount of heavy metal compound it is convenient to use may vary, for example, from 0.5 to 50 parts per million (p.p.m.) by weight preferably 1 to 10 p.p.m., calculated as metal and expressed on the total weight of the organic residue, though larger amounts may, of course, be used, and smaller amounts may be effective if the treatment is prolonged.
- the treatment is effected by heating at temperatures, for example in the range 70° to 200° C., preferably 90° to 130° C., for periods which may vary, for example, from a few minutes, e.g. 5 minutes, to several hours, e.g. 5 hours.
- the treatment may be carried out as a separate step or may conveniently be combined with the removal of at least some of the remaining cyclohexane by distillation.
- a solution of the heavy metal compound may be introduced into the organic residue immediately before it is introduced into a still for fractional distillation of excess cyclohexane from cyclohexanol and cyclohexanone.
- Such distillation may be effected, for example, at temperatures of 100° to 110° C.
- the hold-up time in the still is usually sufficient to bring about decomposition of virtually all the hydroperoxide present.
- the distillation of cyclohexane may take place in more than one stage, and the final removal of cyclohexane may take place by distillation with steam.
- the cyclohexane so recovered may, of course, be recycled to the oxidation.
- Decomposition of the hydroperoxide results in the formation of a mixture of cyclohexanol and cyclohexanone, a cobalt compound favouring a higher proportion of cyclohexanol and a chromium compound a higher proportion of cyclohexanone.
- the mixed cyclohexanol and cyclohexanone remaining may be recovered by distillation.
- the still residues which contain high-boiling impurities and the heavy metal compound may be discarded, and may be disposed of, for example by burning.
- the process of our invention using a said heavy metal compound to decompose the cyclohexylhydroperoxide increases the yield of cyclohexanol and cyclohexanone based on the hydroperoxide present in the oxidate and also based on the cyclohexane converted. Moreover, the process of our invention gives a mixed cyclohexanol and cyclohexanone in which the proportion of monobasic acid impurity, especially of caproic acid is reduced.
- decomposition of the hydroperoxide with a heavy metal compound is many times faster, e.g. 25 times faster, than thermal decomposition, so that decomposition may generally be effected at lower temperatures.
- Chromium octoate, as 0.01% solution in cyclohexane was added to give levels of 5 and 10 p.p.m. of Cr in the treated oxidate, and the rate of decomposition of the peroxide was measured at 100° and 120° C. in stainless steel tubes treated with phosphate to inhibit decomposition of the peroxide by the metal of the tube itself.
- the results, expressed as the half-life of the peroxide, are given in the following Table.
- Example 3 was a repetition of Example 2 except that the heat-soaking treatment was omitted.
- Example 2 was repeated except that the addition of the chromium compound was omitted.
- the yield of distilled cyclohexanol and cyclohexanone attributable to the cyclohexylhydroperoxide in the organic portion after hydrolysis was 85% of the theoretical.
- Other results are given in the following Table 2.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB54424/76 | 1976-12-31 | ||
| GB54424/76A GB1590958A (en) | 1976-12-31 | 1976-12-31 | Oxidation of cyclohexane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US4322558A true US4322558A (en) | 1982-03-30 |
Family
ID=10470967
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US05/857,971 Expired - Lifetime US4322558A (en) | 1976-12-31 | 1977-12-05 | Oxidation process |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4322558A (enrdf_load_stackoverflow) |
| JP (1) | JPS5384941A (enrdf_load_stackoverflow) |
| DE (1) | DE2758759A1 (enrdf_load_stackoverflow) |
| FR (1) | FR2376107A1 (enrdf_load_stackoverflow) |
| GB (1) | GB1590958A (enrdf_load_stackoverflow) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6613946B2 (en) * | 1998-10-22 | 2003-09-02 | Degussa Ag | Process for preparing cyclic alcohols |
| EP1539665A4 (en) * | 2002-09-12 | 2006-07-26 | Invista Tech Sarl | PROCESS FOR THE OXIDATION OF CYCLOHEXANE |
| CN1326819C (zh) * | 2004-11-15 | 2007-07-18 | 中国科学院大连化学物理研究所 | 一种用于环己烷液相空气氧化反应的促进剂及应用 |
| US9156757B2 (en) | 2010-01-21 | 2015-10-13 | Rhodia Operations | Process for the oxidation of hydrocarbons |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0529978U (ja) * | 1991-09-25 | 1993-04-20 | 株式会社相忠 | クーラーボツクス |
| US6814867B2 (en) * | 2002-09-12 | 2004-11-09 | Inuista North America S.à.r.l. | Process for reducing chromium in nonvolatile residue resulting from air oxidation of cyclohexane |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3336390A (en) * | 1965-10-18 | 1967-08-15 | Exxon Research Engineering Co | Saturator for oxidation of hydrocarbons |
| US3419615A (en) * | 1965-03-24 | 1968-12-31 | Exxon Research Engineering Co | Production of cyclododecanol and cyclododecanone |
| US3927105A (en) * | 1968-04-08 | 1975-12-16 | Rhone Poulenc Sa | Process for the preparation of mixtures of cycloalkanols and cycloalkanones |
| US3932513A (en) * | 1971-02-05 | 1976-01-13 | Halcon International, Inc. | Cyclohexane oxidation |
| US3987100A (en) * | 1974-04-11 | 1976-10-19 | E. I. Du Pont De Nemours And Company | Cyclohexane oxidation in the presence of binary catalysts |
| US4042630A (en) * | 1973-10-19 | 1977-08-16 | Stamicarbon B.V. | Process for the preparation of cycloalkanones and cycloalkanols |
| US4058565A (en) * | 1972-12-08 | 1977-11-15 | Bayer Aktiengesellschaft | Process for oxidizing hydrocarbons |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB716820A (en) * | 1951-04-19 | 1954-10-13 | Du Pont | Preparation of oxidized cyclohexane |
| GB777087A (en) * | 1954-05-12 | 1957-06-19 | Du Pont | Improvements in or relating to the oxidation of cyclohexane |
| GB996792A (en) * | 1961-01-31 | 1965-06-30 | Halcon International Inc | Improvements in the production of cycloalkanols and cycloalkanones |
| NL153204B (nl) * | 1966-11-14 | 1977-05-16 | Halcon International Inc | Werkwijze voor het bereiden van een boorzuur-ester van een alcohol. |
| FR1547427A (fr) * | 1967-05-26 | 1968-11-29 | Rhone Poulenc Sa | Perfectionnement à la préparation de mélanges cycloalcanols/cycloalcanones |
| FR1580206A (enrdf_load_stackoverflow) * | 1968-04-08 | 1969-09-05 | ||
| NL7506790A (nl) * | 1975-06-07 | 1976-12-09 | Stamicarbon | Werkwijze voor het bereiden van cycloalkanonen en cycloalkanolen. |
-
1976
- 1976-12-31 GB GB54424/76A patent/GB1590958A/en not_active Expired
-
1977
- 1977-12-05 US US05/857,971 patent/US4322558A/en not_active Expired - Lifetime
- 1977-12-19 JP JP15281177A patent/JPS5384941A/ja active Granted
- 1977-12-29 DE DE19772758759 patent/DE2758759A1/de active Granted
- 1977-12-30 FR FR7739806A patent/FR2376107A1/fr active Granted
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3419615A (en) * | 1965-03-24 | 1968-12-31 | Exxon Research Engineering Co | Production of cyclododecanol and cyclododecanone |
| US3336390A (en) * | 1965-10-18 | 1967-08-15 | Exxon Research Engineering Co | Saturator for oxidation of hydrocarbons |
| US3927105A (en) * | 1968-04-08 | 1975-12-16 | Rhone Poulenc Sa | Process for the preparation of mixtures of cycloalkanols and cycloalkanones |
| US3932513A (en) * | 1971-02-05 | 1976-01-13 | Halcon International, Inc. | Cyclohexane oxidation |
| US4058565A (en) * | 1972-12-08 | 1977-11-15 | Bayer Aktiengesellschaft | Process for oxidizing hydrocarbons |
| US4042630A (en) * | 1973-10-19 | 1977-08-16 | Stamicarbon B.V. | Process for the preparation of cycloalkanones and cycloalkanols |
| US3987100A (en) * | 1974-04-11 | 1976-10-19 | E. I. Du Pont De Nemours And Company | Cyclohexane oxidation in the presence of binary catalysts |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6613946B2 (en) * | 1998-10-22 | 2003-09-02 | Degussa Ag | Process for preparing cyclic alcohols |
| EP1539665A4 (en) * | 2002-09-12 | 2006-07-26 | Invista Tech Sarl | PROCESS FOR THE OXIDATION OF CYCLOHEXANE |
| CN1326819C (zh) * | 2004-11-15 | 2007-07-18 | 中国科学院大连化学物理研究所 | 一种用于环己烷液相空气氧化反应的促进剂及应用 |
| US9156757B2 (en) | 2010-01-21 | 2015-10-13 | Rhodia Operations | Process for the oxidation of hydrocarbons |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2376107A1 (fr) | 1978-07-28 |
| DE2758759A1 (de) | 1978-07-06 |
| JPS6222972B2 (enrdf_load_stackoverflow) | 1987-05-20 |
| DE2758759C2 (enrdf_load_stackoverflow) | 1989-03-09 |
| GB1590958A (en) | 1981-06-10 |
| JPS5384941A (en) | 1978-07-26 |
| FR2376107B1 (enrdf_load_stackoverflow) | 1984-11-16 |
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Legal Events
| Date | Code | Title | Description |
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